Manufacture of lubricating oils



April 3o, 1940.

H. GoETHEl. Er AL MANFACTURE OF LUBRICATING OILS Filed not. 13, 1957 2 Shets-Sheet y1 Ari] 30, 1940' H. GoETHl-:L ET Al. 2.199.200

MANUFACTURE oF LUBRICATING OILS Filed oct. 13, 1937l 2, sheets-sheet 2 Figi J7 vLwaeQW/MM,

Patented Apr. 30, 19404 amazon MaNurAcruna or wmca'rmo oiLsV 'Duisburg-Hamborn, I aul Herbert Goethel,

Schaller, Oberhausen-stormde, and Heinrich Tramm, berhausen-Holten, Germany Application October 13, 1937, Serial No. 168,794 l In Germany October 24, 1936 Claims.. (CL 19E-'18) Our invention relates to lubricating oils and more particularly to an improved method 4of manufacturing same. i f

It is an object of our invention to produce 5 lubricating oils by polymerizing unsaturated hydrocarbons, such as olenes, or hydrocarbon mixtures containing same, by means of a poly- Y merizing catalyst.

It is another object of our invention to improve the manufacture of lubricating oils as disclosed in the 'copending applications for U. S. Letters Patents Serial No. 115,950 led December 15, 1936, by Nikolaus Geiser and Herbert Goethel; Serial No. 115,951 led December 15, 1936, by 1I Heinrich Tramm, and Serial No. 165,566 filed e September'24, 1937, by Carl Clar and Herbert Goethel. -It is known to produce lubricating oils by condensing or polymerizing, by means of a suitable l 4condensing agent or polymerizing catalyst such as a metal halide and more vparticularly aluminium chloride, hydrocarbon mixtures, such as l exceeding plus or minus 1%, to a well defined; curve; oi density. This curve of density estab.

lishes the densities of the individual boiling fractions, in to which the benzine may be divided, in the following manner:` if a benzine suitable for the productionof lubricating oils by polymeriza- .tion is divided into boiling fractions, each of which is distinguished from the other by 10 C., 45 and 1f the density ef the mdividum benzine freetions, each of which corresponds to a boiling range of 10 -C., is ascertained, the values o f density thus obtained must correspond within a limit of error not exceeding 1%, to a curve demean' boiling or distilling temperatures of the individual -fractlons are plotted as abscissae against the corresponding specinc gravities as 55 ordinates:

termined by the following iigures, wherein the l Fraction "f Hydrocarbon .nixtures which contain unsaturated hydrocarbons, but do not obey the law above mentioned, have been found to be less t for the syntheticproduction of lubricating oils. The use of such benzines resulted on the one hand in a low yield of lubricating oil, and on the other hand the lubricating oils obtained showed an unsatisfactory viscosity apex, which means that the viscosity of these lubricating oils depended to a very high degree on the vtempera- `tu1'e*. From benzines, the curves of density of which did not correspond to the .above mentioned conditions, there were obtained yields of from 3 to 28% in lubricating oils, calculated on the quantity of. starting benzine employed,` and these oils showed a viscosity apex of from 2.12 to` more than 4. The yield in lubricating oil as voltt'ained from benzines, the curve of density-of which corresponded to the above mentioned values, was. 42 to 62% and the lubricating oils obtained had a viscosity apex ranging between 1.82 and 1.95. In the process according to this invention the proportion of unsaturated hydrocarbons in the benzine is of minor importance. vThe mixtures to besubjected to polymerization may contain for instance 30% or 50% cr more olenes. Mixtures which contain considerablysmaller quantitles, for instance less than 20%, can also be employed with advantage, provided that they possess the correct curve of density explained above.

Our invention may be illustrated more in detail (Ci. edition, lin 1036.)

by the drawings alxed to this specification and forming part thereof. and by the following examples. Examples 1 and 2 show the behaviour of benzines with curves of density accordingv to our invention, While Examples 3 to 6 show the behaviour of benzines with diierent curves of density. Examples-7 and 8 show the manner in which startingbenzines with a curveof Adensity according to our invention may be obtained.

In the drawings Fig. 1 shows curves of density as defined above. Curve A corresponds exactly to the requirements established by our invention, while curves B and C represent the admissible deviations from the values of density. Curves I to VI show the values of density of the fractions of the benzines which were employed as starting materials in Examples 1 to 6, respectively.

Fig. 2 'is a diagram showing in columns I to VI the averageyields in lubricating oil as obtained according to Examples 1 to 6, respectively,

calculated in per cents of the starting benzine. The superiority, as to yield, of the process according to the present invention can easily be estimated from this gure;

Fig. 3 is a diagram showing in columns I to VI the viscosity apexes of the lubricating oils obtained according to Examples 1 to 6, respectively, while the upper limit of the viscosity apex admissible for a good lubricating oil is indicated by a dotted line. It will be seen that the col.- umns which correspond to Examples 3 to.6, due to the inferior quality of the lubricating oil obtained according to these examples, remarkably exceed this admissible ,upper limit of the viscosity apex.

Example 1 Mean boil' Mean boiling tem- Degt ing tam 3,62%? perature perature 60 0. 655 140 0. m 70 0. 571 150 0. 72S o. 681 0. 7m w 0. 692 170 0. 734 1w 0. 7m 180 0. 738 0. 708 im 0. 741 1m 0. 715 2U) 0. 744 1w o. 7m 210 0. 746

50 grams anhydrous aluminium chloride were stirred 24 hours at 20 C. in an autoclave with 1000 grams of this dried cracking benzine. The mixture obtained by the reactionrconsisted of two layers, viz. ofthe so-called lpper layer, which contains the lubricating oil in dissolved state, and of a lower layer, the so-called contact layer, consisting of double-compounds of aluminium chloride with portions of cracking benzine. rThe upper layer weighed 766 grams; it was washed with caustic soda solution, sulfuric acid and water and thus freed from the remainder of the contact layer and neutralized. After drying the not converted cracking benzine was distilled oi up to a boiling point of 200 C. 'I'he remainderof the distillation was subsequently distilled at 200 C. in vacuo-at an abso- .lute pressure of 5 mms. mercury column, whereby the lubricating oil was recovered as distillation` residue. There were obtainedl407 grams lubricating oil with a density of 0.859 at 20 C.

and a viscosity of 17.3 E. (Engler) at 50 C. The viscosity apex was 1.9, while the solidifying point was -23. y

The contact layer weighing 283 grams was reacted in the same manner at 55 C. in an autoclave with 1000 grams fresh cracking benzine of the 'same quality. The upper layer thus obtained weighed 803 grams and contained 450 grains lubricating oil. The contact layer the weight of which had increased to 480 grams, was reacted anew at 95 C. in the autoclave with 1000 grams freshcracking benzine. There followed similar reactions at 110, 130 and 150 C.

The following table shows the details of these tests:

Reaction N 0.-

Temperaturadegrees.- 20 55 95 110 130 150 Quantity of cracking benzine started from grams.- 1,(l0 1,000 1.000 1,000 1,000 1,000

Contact layer before L'S50 conversiongrams.. Al la) 283 480 510 470 520 Contact layer after c0nversion.'-grams. 283 Y 480 510 470 520 550 Upper layer. .-.do. 766 803 968 1,040 945 969 Quantityoilubricating oil obtained grams.. 417 450 5w 610 480 520 The same in percents of the quantity of starting benzine' 41.7 45 55 61 48 52 Density at 20 C 0. 859 0.856 0. 65 0.868 0.866 0.865 Viscosity at 50 C E.. 17.3 16 19. 1 19. 6 18. 6 Viscosity apex 1.9 1.82 .88 1.95 1.88 1.92

Example 2 As starting material there was used again a benzine obtained by cracking the fractions, boiling above C., of a hydrocarbon mixture produced by the reaction of carbon monoxide with hydrogen. 'I'his cracking benzine showed the 'following density curve.

15 kilograms of this cracking benzine were stirred, in an autoclave of 50 liters, first 4 hours at 20 C. and thereafter 8 hours at 50 C. together with 200 grams fresh aluminium chloride and 11,15'0grams of a contact layer, which had been formed in -the course of 30 preceding single reactions and contained aluminium-chloride duble-compounds. The upper layer formed after the mixture had been allowed to settle, weighed temperature and time with 15 kilograms fresh cracking benzine.

` Any optional number of conversions may be carried out with fresh quantities of cracking benzine, the contact layer obtained in the preceding conversion treatments beingreused.

conversion was carried out 4 hours at 20 C. and

subsequently 8 hours at 50 C.:

Reaction No.

Quantityoicrackinghenzine started fromm.

grams-- 16,000 15,000 10.000 15,000 15,000 Addition oi fresh A101 e-- grams.. 200 200 200 200 m0 Contact layer before conv a 11,150 11, 750 12, 450 12,800 12,600 Contact layer alter conversion gi-ams.. il, 550 12, 250 12, 600 12, 400 13, 050 Upper layer .do- 14, 800 14. 500 14, 850 15, 400 14, 550 Quantity oi lubricating olobtain 9,060 8,760 8,700 9,240 8,720 The same in per cents oi the quantity 0i startv lng benzine 60.4 58.4v 58 01.0 58. 1 Density at 21 C 0. 860 0.859 0.860 0. 858 0.860 Viscosity at 50 0...? E.. 13. 38 14. 70 17.42 13.88 12.2 Viscosity apex 1.9 1.88 l. 92 1.9 l. 88

Example 3 As starting material was used a cl'acitingbcn-A zine obtained according to the so-cailed TVP- process* from the higher boiling hydrocarbons producedl in a benzine synthesis according to Fischer and Tropsch, and which showed the following values of density.

Mean boir- Mean beil- Dcnsit Densit ing tem ering temperstun? at 20 ature at 20 sa an* ...n D... tamper-aatm tempera atmg.

ture tum 00 0000 100 0.141 00 0.011 140 0.145 10 0.084 150 0.140 a0 i 0.001 100 0.155 0.711 170 0.700 100 0.120 iso v0.105 0.130 100 0.110 100 0.100l f In the mannerdescribed in Example l there were carried out with this cracking benzine conversions at 20, 40 and 70, respectively, and

there was againobtained an unsatisfactory yield of lubricating oils which moreover showed too high viscosity apexes. `The following table shows the details of the' test:

Reaction number Quantity oi cracking benzine started om l, 000 1, 000 1, 000 Contact layer before conversion..

ms.- (50 A1011) 179 198 Contact layer alter c0nversion do 179 198 245 Upper yer 0.... 875 980 951 Quantity oi lubricating oli obtained.

grams.- 280 180 229 The same in ggf cents oi' the quantity A of starting naine 28 18. 6 22. 9 Density at Z1 C. 0.804 0. 900 0. 907 Viscosity at 50 O 34 172 51 Viscosity apex 2. l2 3. 7 3. 25

Example 5 servedas starting material:

In the manner described in connection with Example 1 there were successively carried out three Mean beu-- mit Mean boil- Density conversions with this cracking benzine at 20, 40 Lateg etzow 'gfg ai 20 c and 70 C., respectlvely.- -The reaction lastedy in f each case 24 hours. There were obtained only .C small yields o flubricating oil having too 'high 00 0.008 120 0.131 viscosity apexes. The details of the tests arel g3 313g 313g compiled in the following table: `00 0.100 '150 0.104 100 0.111 100 0.113 110 0.121 110 0.180

Reaction number '1 2 3 The conversions took place, in the same way as 1 in Example 1, at 20, 55 and 95 C. respectively. Quantityofmckngbenne stm-ted The yield of lubricating oil was however parroin ams.- 1,000 1,000 1,000 Contactin more comm on ticularly small and the oils showed a viscosity C y grams-- (501101.) 220 240 apex ranging from 2.45 to more `than 4. The 32 ggg details of the tests may be estimated from the Quantity of lubricating oil obtained f0110w1l18 table:

. grams.. 223 171 232 The snmehilnptareents ofthe quantity 22 3 i7 1 23 2 0 S BI g 1111110 Density er 20 0. 882 0. ses 0. sez mmm N' Viscosity at 50 C. E 49 66 22 Viscosity apex 3.03 3.25 3.12 1 2 3 E:i:ample4y I Qnenu er wenn benzine startetlrom.--- ams.. 1,000 1,000 1,000 As startingy material was used again a crack Contact layer before conversion (5o MCI) 1w 90 m5-. 1 mg benzine produced acordng t0 the TVP' Contact layer after conversion process from the higher boiling hydrocarbons obgrams.. 100 00 l.

tained in a benzine synthesis according to gfilwi',gim; 88s 1069 "00 Fischer-Tropsch, and which showed the follow- ,mtlrinedmi 6-36). m 77 53 37 551110 11])010611 8 e 11811- ing values of density. my ofsmtn bem, o o g 0 *(Th True-vapour-phase"fprocess as described for ini* '17.5 77.6 l 39 stance in pages 430-431,'vo1. 15,01 Redner and Natural 3.6 2.45 Above4 Gasoline Manufacturer," or in British Patent 340,021.

CO to H2 may vary in the gas used for the syn- M bou thesis. If its content of carbon monoxide is inintmper1Deml ilgtgnfgl; Density creased, a benzine is obtained which is richer in Mure am.) amro 2 C' -unsaturated hydrocarbons than the benzines which are usually obtained from a synthesis gas 532 o C'.

with a proportion of co to H2 equal to 1:2. In o 3% g3. 3;;3 any case the reduction of the carbon' monoxide g3 ggg 1% 0.725 yields, gin addition to gaseous hydrocarbons, a 90 jm .150 gj?? product of reaction consisting of liquid hydro- 100 0.705

carbons and solid hydrocarbons which are dispreferred. The period of time during which the hydrocarbons are caused to remain in the cracking zone depends on the boiling range ofthe Example 6 In the same manner as in Example 1 there were carried out successive conversions at 20, 50 and 80 C., respectively, with a benzine having the following density values: pera'imre used and varies between about 3 and 15 minutes. For hydrocarbon mixtures of a similar boiling range the time of cracking .is the hirnmgl' 39%? hgltgflig' shorter, the higher the cracking temperature Demme Demme chosen. lSuitable benzines may be obtained aco cording to the following two examples.

C' so o. 647 c"1ro 0.704 Example 7 so 0.657 13o 0.111 gg ggg g3 A hydrocarbon mixture boiling above 180 C. 90 01684 160 01m and obtained in the catalytic hydrogenation of 03 (0)- 231; gg 8- carbon ,monoxide according to Fischer and Tropsch is led under a pressure of10 atmospheres above normal through cracking tubes heated to 490 C. The products are caused to remain in the cracking zone 6-7 minutes. 'I'he return-proportion, i. e., the proportion of the freshly introduced hydrocarbon oils coming from the hydrogenation of the carbon monoxide, to the not cracked portions of hydrocarbon which are recycled, is 1 to 4.5. From the cracking benzines The starting material was a hydrocarbon mixture boiling between 150 and 180 C., obtained as primary product ina synthesis according to Fischer and Tropsch. The yield of lubricating oils was small and the oils obtained showed a viscosity apex of approximately 2.5. The details of the tests are compiled in the following table: thus obtained there is separated a fraction boil- Rmtion No ing from 30 up to 180 C. The cracking benzines contained in this fraction correspond to l 2 3 the curve of density according to our invention, v as may be seen from the following data:

Quiirltsietff of cracking benzine 1 00o 1 000 1 ooo s rom -grams-. Mean boil- Mean boil- Contact la er before conversion DODS Den-Sit y gram (5011101.) 14o 21o ngatepe' atar. Mattig?" aard'. Contact layer after conversiomdo. 140 210 230 Upper layer 910 930 980 Quantity of lubricating oil obtained C C, grains-- 100 7 130 5o o. 651 12o o. 12o The same in er cents oi the quantity 60 0 653 130 0, 725 of starting enzine 10 7.5 13 70 0.577 140 0,732 Density at 20 C.. 0. 848 0. 844 0. 848 80 (1 583 150 0 736 Viscosity at 50 C.. 12. 7 12. 8 5. 4 l 90 0 699 160 0. 740 Viscosity apex. 2. 32 2. 5 2. 44 100 0. 707 170 0. 745 11o 0.714 18o 0.149 We will now describe more in detail some ways according to which hydrocarbon mixtures may Eamle 8 e be obtained which possess curves of density as prescribed in the process of our invention. The mixtures are' obtained as a rule by` a cracking reaction from hydrocarbon oils produced by the hydrogenation of 'carbon monoxide.

The benzine synthesis takes place in the usual manner, for instance by contacting at ISO-200 C. and un'der ordinary pressure a mixture of one part CO and two parts H2 with a cobalt-thorium-kieselguhr catalyst composed for instance of 37.3% Co, 6.7% ThOi and 56% kieselguhr. A cobalt-magnesium-catalyst or av cobalt-catalyst activated by anaddition of thorium and magnesium may be used as well. The proportion of boils from 30 up to 150 C., corresponds to the curve of densities according to our invention, as may be estimated from the 'following iigures:

solved in the liquid ones.A Slightly increased pressure, for instance of 7-8 atmospheres, may be employed instead of ordinary pressure; in, this case the proportion of solid hydrocarbons in the product of reaction is increased.

Benzires having a curve of density such as ref` quired in our process maybeobtained from thes'eoypresent invention, all the Idetails of operation synthetic hydrocarbon mixtures by a cracking may be made .use of which were` disclosed in the reaction. Cracking temperatures of between above-mentioned copending applications Serial 450 and550 C., preferably of 460 to 510 C., are Nos. 115,950, 115,951 and 165,566. Thus during When producing lubricating oils in the presence yofa polymerization catalyst, such as alumixture which contains; a suflicient proportion of unsaturated hydrocarbons, such as olenes,

starting hydrocarbons and on the cracking temof freshhydrocarbns added to the recycled nonconverted hydrocarbonsis 1 to 3.7. Of 'the cracking benzines thus obtained the fraction -which .and possesses the curve of density defined by the minium chloride, from a benzine or hydrocarbon l polymerization the temperature may vary within wide limits, for instance between about 0 and 160 C. It is preferably raised, in stages or continuously, in the course of polymerization as described more in particular in the copending applications Serial Nos. 115,950 and 115,951. The polymerization treatment may last about 12-24 hours for a charge to be polymerized at practically constant temperature, but it may last as much as 120 hours if the continuoustreatment disclosed in the copending application Serial No. 115,951 is employed. The quantity of aluminium chloride may amount up to about 6%, calculated on the hydrocarbon mixture treated in the ilrst charge; small quantities, about 0.5-2%, may be added in order to revive the aluminium chloride sludge formed in the polymerization treatment out as a rule in an autoclave, the pressure of opn eration is substantially the total vapor pressure of the substances under treatment at the operating temperature. In the course of polymerization the pressure drops in proportion as larger molecules are formed from the denes.

Various'changes may be made in the details disclosed in the foregoing speciiication without departing from the invention or sacriiicing the advantages thereof. j

We claim: v l

1. The method of producing lubricating oil from a cracked benzine mainly consisting of aliphatic hydrocarbons and rich in olenes, which comprises subjecting for at least about l2 hours to the action of a metal halide polymerizing catalyst, present in a starting proportion of about up to 6%, at temperatures not materially above about 160C., a cracked benzine of the aforenoted type, the ten degrees C. range fractions of which have densities which, with deviations not exceeding 1% in either direction, are related to the respective mean distilling temperature as Afollows: v

2. The method o! producing lubricating oil from a cracked benzine mainly consisting of aliphatic hydrocarbons and rich in olenes, which comprises subjecting for at least about 12 hours to the action of a metal halide polymerizing cattions not exceeding 1% in either direction, are related to the respective means distilling temperature as follows:

Mean dis- D i Mean dis- D i tilling temem t tilling tem- 50W pexature at m perature m C 3. The method of claim 1, wherein aluminium chloride is employed as polymerization catalyst.-

4. The method of claim 1, in which the benzine subjected to the action of the polymerizing catalyst is produced by the steps of reacting lhydrogen with carbon monoxide in the'presence of a. hydrogenating catalyst to produce a hydrocarbon mixture of the type of synthetic benzine and of cracking the hydrocarbon mixture thus obtained at a temperature ranging 'between about 450 and 550C. under slightly increased pressure.

5. The method of claim 1, in which the benzine subjected to the action of the polymerizing catalyst is produced by the steps of reacting hydrogen with carbon monoxide in the presence of a hydrogenating catalyst activated by cobalt to produce a hydrocarbon mixture oi the type of synthetic benzine and of cracking the hydrocarbon mixture thus obtained by maintaining same about 5-15 minutes at a temperature ranging between about 460 and 510 C. under a pressure of approximately 10 atmospheres.

. HERBERT GOE'I'HEL.

PAUL SCHAILER. HEINRICH TRAMM. 

